CN1837251A - Aqueous copolymer dispersions with reactive diluents - Google Patents

Aqueous copolymer dispersions with reactive diluents Download PDF

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CN1837251A
CN1837251A CNA2006100595968A CN200610059596A CN1837251A CN 1837251 A CN1837251 A CN 1837251A CN A2006100595968 A CNA2006100595968 A CN A2006100595968A CN 200610059596 A CN200610059596 A CN 200610059596A CN 1837251 A CN1837251 A CN 1837251A
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hydroxyl
gram
functional
copolymer dispersion
methyl
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S·霍法克
M·梅希蒂尔
T·蒙茨梅
N·尤瓦
R·格特兹曼
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Covestro Deutschland AG
Bayer Intellectual Property GmbH
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

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Abstract

The invention relates to an aqueous copolymer dispersion comprising: A) one or more hydroxy-functional copolymers, and B) one or more hydroxy-functional polycarbonate polyols as reactive diluents, wherein A) is synthesized from a), B), c) and d): a) one or more OH-free (meth) acrylates and/or vinylaromatic compounds, b) one or more hydroxy-functional (meth) acrylates, c) one or more ionic and/or potentially ionic monomers capable of undergoing a free-radical copolymerization, and d) one or more optional monomers capable of undergoing a free-radical copolymerization, which are different from components a) to c). The invention also relates to a process for preparing these aqueous copolymer dispersions and to their use in coating compositions.

Description

Aqueous copolymer dispersion with reactive thinner
Background of invention
Technical field
It is low and based on aqueous copolymer dispersion of hydroxyl-functional multipolymer and preparation method thereof to the present invention relates to solvent, and the binder composition and the application of this tackiness agent in preparation scrath resistance coating that contain this aqueous copolymer dispersion.
Background technology
In coating system (for example, DE-A 3209421, EP-A 95263, EP-A 105293, EP-A 133949, EP-A 288763 described in), use water-dilutable and be known based on the tackiness agent of multipolymer.But these tackiness agents generally comprise and are used for stable emulsifying agent and/or the organic cosolvent of quite a few.
Using considerable organic solvent is disadvantageous for environmental protection.But, in polymer manufacture, guarantee enough agitatabilities, remove the purpose of the certain minimum charge amount (fill level) of the heat of reaction mixture and reactor in order to reach, with an organic solvent be inevitable.In addition, in water-based paint compositions, organic solvent can bring favourable effect, for example improves the optical property and the levelling property of stability in storage, pigment wettability, film.
The content that reduces solvent relevant with operation in multipolymer or the copolymer dispersion subsequently needs the equipment and the energy, and the higher cost in cost aspect, therefore need and not prepare aqueous polymer dispersion under with an organic solvent the condition basically, and can not make its degradation simultaneously.
Method by chemical reaction is solidified, for example, by with aminoresin or end-blocking or not end capped polyisocyanates reaction solidified copolymer dispersion, must contain a certain amount of active group, such as hydroxyl.These groups are generally by using hydroxyl-functional (methyl) acrylate to introduce in the multipolymer in copolyreaction.But, to compare with non-sense (methyl) acrylate or vinylbenzene, these hydroxyl-functional raw materials are very expensive.And, compare with the multipolymer in the organic solution, need usually to use considerable these raw materials, to come the wetting ability of compensating coating film by bigger cross-linking density.
A kind of method that can avoid basically using solvent can prepare hydroxyl-functional secondary (secondary) copolymer dispersion again in polyreaction is disclosed among the EP-A 0758007.Normally used solvent is all or part of to be substituted by the hydroxyl-functional polyethers.The hydroxyl-functional polyethers is stayed in the secondary dispersion as reactive thinner, and forms the crosslinking reaction of carbamate after being present in end capped or not end capped isocyanate reaction.Therefore, they are for not influence of VOC.But known to some Application Areas, polyether component is used in and can causes relatively poor tolerance performance in the coating composition, and for example, scrath resistance is relatively poor.
Have now found that, if the hydroxyl-functional polycarbonate as reactive thinner, then low and aqueous copolymer dispersion coated membrane better tolerance (particularly You Yi scrath resistance and acid resistance) of solvent can be based on the hydroxyl-functional multipolymer.
Summary of the invention
The present invention relates to a kind of aqueous copolymer dispersion, it contains:
A) one or more hydroxyl-functional multipolymers and
B) one or more are as the hydroxyl-functional polycarbonate polyol of reactive thinner, wherein, A) by a), b), c) and d) come synthetic:
A) one or more do not contain (methyl) acrylate and/or the vinyl aromatic compounds of OH,
B) one or more hydroxyl-functionals (methyl) acrylate,
C) ionic and/or the potential ionic comonomer (potential ionic monomer) of free radicals copolymerization reaction can take place in one or more, and
What d) one or more were optional is different from component a) to c) the monomer that free radicals copolymerization reaction can take place.
The invention still further relates to that a kind of one or more contain a) by making, b), c) and monomer mixture d) at one or more hydroxyl-functional polycarbonate polyol B as reactive thinner) in the presence of carry out Raolical polymerizable, multipolymer with gained was dispersed in the water before or after adding neutralizing agent subsequently, the method for preparing copolymer dispersion of the present invention, wherein
A) do not contain (methyl) acrylate and/or the vinyl aromatic compounds of OH for one or more,
B) be one or more hydroxyl-functionals (methyl) acrylate,
C) ionic and/or the potential ionic comonomer of free radicals copolymerization reaction can take place for one or more, and
D) be different from component a) to c for one or more are optional) the monomer that free radicals copolymerization reaction can take place.
The invention still further relates to the coating composition that contains aqueous copolymer dispersion of the present invention, and by the prepared scrath resistance coating of these coating compositions.
Embodiment
As component monomer a) is acrylate and the methacrylic ester (hereinafter being called (methyl) acrylate) that 1-18 carbon atom arranged in the alcohol moiety of ester group.Alcohol moiety can be linear aliphatic, side chain aliphatic series or alicyclic.
Suitable monomers a) comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isopropyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the isomers of (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid stearyl or (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 3-methyl cyclohexanol ester and (methyl) isobornyl acrylate or (methyl) vinylformic acid acetoacetoxy groups (acetoacetoxy) ethyl ester.Particularly, suitable vinyl aromatic compounds comprises the vinylbenzene and the Vinyl toluene of vinylbenzene, replacement.Also suitable component is the mixture of above-claimed cpd a).
Suitable components b) comprise that ethylenic is undersaturated and contain the monomer of OH, such as the hydroxy alkyl ester of unsaturated carboxylic acid, preferably hydroxyalkyl has (methyl) hydroxyalkyl acrylate of 2-12, preferred 2-6 carbon atom.Example comprises isomers, (methyl) vinylformic acid 2-, 3-and the 4-hydroxy butyl ester of (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) Propylene glycol monoacrylate and the isomers of the own ester of (methyl) vinylformic acid hydroxyl.
Ionic and/or potential ionic comonomer c) be those monomers that Raolical polymerizable can take place, comprise ethylenically unsaturated monomers with carboxylic acid or carboxylic acid anhydride group.Example comprises the mono alkyl ester such as the maleic acid mono alkyl ester of vinylformic acid, methacrylic acid, acrylic acid β-carboxylic ethyl ester, Ba Dousuan, fumaric acid, maleic anhydride, methylene-succinic acid or diprotic acid and/or acid anhydrides, preferably vinylformic acid and/or methacrylic acid.
Other suitable monomers c) is undersaturated and has the compound that Raolical polymerizable can take place of phosphoric acid ester, phosphonic acid ester, sulfonic acid or sulfonate ester group, for example WO-A 00/39181 (p.8,1.13-p.9,1.19) described in, 2-acrylamido-2-methyl propane sulfonic acid preferably.
Also can use other monomer that free radicals copolymerization reaction can take place as component d).Example comprises the derivative of acrylic or methacrylic acid, such as acrylamide, Methacrylamide, vinyl cyanide and methacrylonitrile; Vinyl ether; And vinyl-acetic ester.Other suitable monomers d) comprises that functionality is more than or equal to 2 (methyl) acrylate monomer and/or vinyl monomer, such as two (methyl) vinylformic acid hexylene glycol ester or Vinylstyrene.Other suitable monomers d) is with the oxirane modification or increases polymerisable hydroxy functional monomers chain, number-average molecular weight≤3000 gram/moles (preferred≤500 gram/moles).Be preferably oxyethane, propylene oxide or butylene oxide ring as this oxirane that needs, they can use or mix use separately.
Other monomer d) comprise for example vinyl ester of tertiary carbon (Versatic) acid, it can trade(brand)name VEOVA TM9,10 and 11 buy (from Resolution Performance Products).They are vinyl ester of general formula (I) with high branched structure,
Wherein, R 2And R 3Be the branched-chain alkyl that has 6,7 or 8 carbon atoms altogether, R 4It is methyl.These acid are corresponding to VEOVA TM9,10 and 11 acid.
The second-order transition temperature of the homopolymer of VEOVA series (Tg) is 70 ℃ (VEOVA 9) ,-3 ℃ (VEOVA 10) and-40 ℃ (VEOVA 11) according to reports.
Other monomer d) comprises alkoxyl group polyoxyethylene glycol (methyl) acrylate or alkoxyl group polypropylene glycol (methyl) acrylate, those compounds that obtained by acrylic or methacrylic acid and oxyethane polyethers or propylene oxide polyethers generation esterification for example, wherein polyethers is by a kind of preparation in the isomers of monofunctional alcohol such as methyl alcohol, ethanol, (Virahol) or butanols.Alkoxyl group polyoxyethylene glycol (methyl) acrylate preferably.
Suitable hydroxyl-functional polycarbonate polyol B) preferably those by monomeric diol (such as, 1,4-butyleneglycol, 1,6-hexylene glycol, glycol ether, triglycol, Tetraglycol 99, dipropylene glycol, tripropylene glycol, four propylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 4,4 '-hydroxymethyl-cyclohexane and/or their mixture) and diaryl carbonate (such as, diphenyl carbonate), dialkyl carbonate (such as, methylcarbonate and diethyl carbonate), alkylene carbonates (such as, ethylene carbonate or Texacar PC) or the prepared compound of phosgene reaction.Randomly, can use the functional monomer polyvalent alcohol of a small amount of height, such as TriMethylolPropane(TMP), glycerol or tetramethylolmethane.
Hydroxyl-functional polycarbonate polyol B) average hydroxy functionality is 1.6 to 6, is preferably 1.8 to 3, more preferably 1.9 to 2.3, and number-average molecular weight is 240 to 5000, is preferably 500 to 3000, more preferably 700 to 1500.Polycarbonate polyol B) preferably prepares by the preparation method described in EP 1404740B1 (6-8 page or leaf, embodiment 1-6) and the EP1477508A1 (page 5, embodiment 3).
Particularly preferred polycarbonate polyol B) by 1,4-butyleneglycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, the mixture of two kinds of alcohol is obtained in 5-pentanediol or the above-mentioned glycol, and the average hydroxy functionality is 1.9 to 2.05.
In component A) and weight B) be benchmark, B component) amount be generally 5 weight % to 60 weight %, be preferably 10 weight % to 40 weight %, more preferably 15 weight % to 30 weight %.
The step of polymerization of unsaturated monomers is known, comprises adding reactive thinner B in reactor) as initially feeding intake, use radical initiator polymerization unsaturated monomer.Copolyreaction is general preferred to be carried out under 40 ℃ to 200 ℃, more preferably carries out under 60 ℃ to 180 ℃, most preferably carries out under 80 ℃ to 160 ℃.
Randomly, can be on a small quantity with an organic solvent, suitable solvent comprises known those solvents in the coating technology, such as the mixture of alcohol, ether, the alcohol that contains ether, ester, ketone, non-polar hydrocarbon or these solvents.The consumption of solvent should make its amount account for 0-5 weight % in final dispersion.If desired, the solvent of use can partly be removed by distillation again.
The example that is used for the suitable initiator of polyreaction comprise organo-peroxide (such as, di-t-butyl peroxide or t-butyl peroxy 2-ethylhexanoate) and azo-compound (such as, Diisopropyl azodicarboxylate (AIBN)).The consumption of initiator is decided according to required molecular weight.For the reliability of operating be easier to handle, peroxide initiator can be used as the solution form, solvent is the organic solvent of suitable the above-mentioned type.
One of the inventive method preferred embodiment in, in B component) in the presence of carry out unsaturated monomer two steps add and polymerization.In this embodiment, in the first step (I), by the component of 55 weight % to 90 weight % a), 2.5 the components b of weight % to 50 weight %), the amount of component b of 0 weight % to 6.5 weight %) and the component d of 0 weight % to 42.5 weight %) make the hydroxyl-functional multipolymer, the OH value (OHnumber) of this multipolymer is a 12-200 milligram KOH/ gram solid, preferred 15-190 milligram KOH/ gram solid, more preferably 100-165 milligram KOH/ restrains solid, acid number (acid number) is a 0-50 milligram KOH/ gram solid, preferred 0-20 milligram KOH/ gram solid, more preferably 0-15 milligram KOH/ gram solid.
In next step (II), make another kind of polymkeric substance in the reaction mixture that monomer a)-d) makes in by step (I).The OH value of this polymkeric substance is a 20-200 milligram KOH/ gram solid, preferred 20-190 milligram KOH/ gram solid, more preferably 50-165 milligram KOH/ restrains solid, and acid number is a 50-200 milligram KOH/ gram solid, preferred 75-185 milligram KOH/ gram solid, more preferably 77-150 milligram KOH/ gram solid.The polymkeric substance that makes in the step (II) by the component of 45 weight % to 80 weight % a), the components b of 5 weight % to 50 weight %), the amount of component b of 6.5 weight % to 25 weight %) and the component d of 0 weight % to 43.5 weight %) make.
In this two step, for every kind of polymkeric substance, it is 100 weight % that the % numerical value that polymkeric substance is formed is added up.Amount of monomer to two kinds of polymer products is selected, and makes that be 10: 1 to 1: 2 from the polymkeric substance of step (I) to the weight ratio from the polymkeric substance of step (II), preferred 6: 1 to 2: 1.
Synthetic component amount a)-d) preferably makes the OH value of multipolymer be 12.5-200 milligram KOH/ gram solid, be preferably 15-190 milligram KOH/ gram solid, more preferably 95-165 milligram KOH/ restrains solid, acid number is a 4.5-150 milligram KOH/ gram solid, be preferably 7-75 milligram KOH/ gram solid, more preferably 10-60 milligram KOH/ gram solid.Step (I) and (II) polymkeric substance of gained make by following component: the component of 54 weight % to 83 weight %, preferred 53.5 weight % to 87 weight % is a); 2.5 the components b of weight % to 50 weight %, preferred 3 weight % to 50 weight %); 0.6 the amount of component b of weight % to 19 weight %, preferred 1 weight % to 12.5 weight %); And the component d of 0 weight % to 43.5 weight %, preferred 0 weight % to 43 weight %).
Can use operate continuously (gradient polymeric) to replace the multistep polymerization method, by add forming with one or more copolymer A) the monomer mixture that changes of composition carry out operate continuously.Amount of component b) and optional d) the percentage of hydrophilic monomer percentage when preferably the percentage when reinforced the end is higher than reinforced beginning.
The number-average molecular weight Mn of the multipolymer that makes by the inventive method is a 500-30000 gram/mole, is preferably 1000-15000 gram/mole, more preferably 1500-10000 gram/mole.
In the hydroxyl-functional copolymer A) be dispersed in the water before, when being dispersed in the water or after being dispersed in the water, be converted into the form of its salt by adding the acid groups that there is at least a portion in suitable neutralizing agent.Suitable neutralizing agent comprises organic amine or water-soluble mineral alkali, such as soluble metal oxyhydroxide, metal carbonate or alkali metal bicarbonate salt.
The example of suitable amine comprises N-methylmorpholine, triethylamine, ethyl diisopropyl amine, N, N-dimethylethanolamine, N, N-dimethylisopro panolamine, N methyldiethanol amine, diethylethanolamine, trolamine, butanolamine, morpholine, 2-amino methyl-2-methylpropanol or isophorone diamine.In mixture, also can correspondingly use ammoniacal liquor.Particularly preferably be trolamine, N, N-dimethylethanolamine and ethyl diisopropyl amine.
The add-on of neutralizing agent should make and 40% to 150% of the theoretical degree of neutralization that reaches acid groups be preferably 60% to 120%.The neutral degree is interpreted as in the adding and the base groups of component and the ratio between the acid functional group in the multipolymer.The pH of aqueous adhesive dispersions of the present invention is 6-10, preferred 6.5-9.
The solids content of aqueous copolymer dispersion of the present invention is 25 weight % to 70 weight %, be preferably 35 weight % to 60 weight %, 40 weight % to 55 weight % more preferably, the content of organic solvent is 0 weight % to 5 weight %, is preferably 0.5 weight % to 3.5 weight %.
Copolymer dispersion of the present invention can be used to prepare water-based paint compositions.By (depend on activity or randomly linking agent is carried out end-blocking) made up in they and linking agent, can form single component or double-component paint composition.For the present invention, one-component coating compositions is a kind of like this coating composition, and binder ingredients and linking agent component can store together in the said composition, and quite big degree can not take place or to subsequently any disadvantageous crosslinking reaction that is coated with.Crosslinking reaction only when applying or after applying, takes place in linking agent activation back.This activation can realize by for example elevated temperature.
For the present invention, double-component paint composition is a kind of like this coating composition, and binder ingredients and linking agent component in the said composition must be stored in respectively in the different containers because have high reactivity.These two kinds of components are only just mixed applying not long ago, and they generally do not need other activation to react.In order to accelerate crosslinking reaction, also can use catalyzer or adopt comparatively high temps.
The invention still further relates to a kind of water-based paint compositions, it contains:
I) one or more aqueous copolymer dispersions of the present invention, and
Ii) at least a OH-active crosslinker.
The example of suitable OH-active crosslinker comprises polyisocyanate crosslinker, acid amides-formaldehyde resin and amine-formaldehyde resin, resol, air aldehyde resin and ketone resin, such as resol, resole, furane resin, urea resin, carbamate resins, cyanate resin, melamine resin, benzo guanamine resin, ammonia cyanogen resin and aniline resin.
Preferred cross-linking agents is 2 or more a plurality of isocyanate groups to be arranged and by for example isophorone diisocyanate, 1 in each molecule, hexamethylene-diisocyanate, 1,4-two isocyanato-hexanaphthenes, two (4-isocyanato-hexanaphthene) methane, 1, the toluene 2 of 3-two isocyanato-benzene, three isocyanato-nonanes or isomers, 4-and 2, the polyisocyanates that 6-vulcabond (TDI) makes.Polyisocyanates also can contain carbamate (urethane), isocyanuric acid ester and/or biuret group.It is end capped that polyisocyanates can be chosen wantonly.
Particularly preferredly be to use polyisocyanates low viscous, that make by aliphatic series or alicyclic isocyanate.Randomly, these polyisocyanates also can be hydrophilic.
The viscosity that is used as the polyisocyanates of linking agent is preferably 23 ℃ of following 10-5000mPa.s, in order to regulate viscosity, also can be used as the mixture that forms with a small amount of inert solvent and uses.
Multipolymer of the present invention generally is enough hydrophilic, even hydrophobic cross-linking agent resin also can disperse under the situation that does not add other emulsifying agent.But this does not get rid of the external emulsifying agent of use.
The polyisocyanates that maybe can be scattered in the water soluble in the water can make by for example carrying out modification with carboxylicesters, sulphonate and/or polyoxyethylene group and/or polyoxyethylene/polyoxypropylene.The hydrophilic modification of polyisocyanates can be by for example carrying out with the monohydroxy Hydrophilicrto polyether alcohol reaction below the stoichiometry.The preparation example of this type of hydrophilic polyisocyanates is as being described among the EP-A 0540985 (p.3,1.55 to p.4,1.5).
Also most suitable polyisocyanates be described in EP-A 959087 (p.3, in 11.39-51), contain allophanate groups and under the condition of allophanic acid esterification, react the polyisocyanates that makes by the polyisocyanates and the polyoxyethylene Aethoxy Sklerol of low-monomer-content.Also suitable is to be described in DE-A10007821 (p.2,1.66 extremely p.3,1.5) in, the water dispersible polyisocyanate mixtures that makes by three isocyanato-nonanes, and the hydrophilic polyisocyanate that contains ionic groups, for example DE-A10024624 is (p.3, described in 11.13-33).
Also can use the mixture of different cross-linking agent resins.
Before aqueous copolymer dispersion preparation of the present invention, when preparing or after the preparation, can add known additives in the coating technology, for example defoamer, thickening material, pigment, dispersing auxiliary, catalyzer, anti, antisettling agent or emulsifying agent.These additives also can join in the coating composition that contains aqueous copolymer dispersion of the present invention.
For example, the water-based paint compositions that contains aqueous copolymer dispersion of the present invention is applicable to that all need water-based paint compositions to meet in the Application Areas that strict membrane stabilities require.Coating composition can be used to be coated with surface, coating and the sealing timber of mineral construction material and based on the material of timber, coating metal surfaces (metallic coating), to pitch with asphalt surface is coated with and the various frostings of japanning, coating and sealing (plastic coating), and is used for high-gloss varnish.
The water-based paint compositions that contains aqueous copolymer dispersion of the present invention be applicable to produce industrial coating for example automobile OME modifies or the trimming field in used low solvent priming paint, surfacer, painted or transparent finish paint material, transparent coating material and high-gloss varnish, and can be separately and the single coating material that applies continuously.Aqueous copolymer dispersion of the present invention is particularly suitable for producing and is used for the aqueous transparent coated material that automotive OEM is modified, and needs height endurability energy, for example scrath resistance and chemical resistant properties this moment especially.
The invention still further relates to a kind of method for preparing coating, will contain in the method on the coating composition paint base material of the bright copolymer dispersion of we, with after fixing.The coating of gained residual gloss behind levelling again surpasses 90%.
Coating composition of the present invention generally 0 ℃ to 180 ℃, preferred 18 ℃ to 160 ℃, more preferably solidify under 40 ℃ to 140 ℃ the temperature.
Can use single component or optional bi-component spray automatic doubler surface glouer, prepare coating by various spraying methods, for example compressed air spraying, hydraulic spraying or electrostatic spraying.Also can utilize other method to apply the coating composition that one or more contain hydroxyl-functional aqueous copolymer dispersion of the present invention, for example spread-coating, roller coat or blade coating.
Embodiment
Except as otherwise noted, all percentage ratios are weight percentage.
According to DIN53019, use the PhysicaViscolab of the Physica supply of material of German Stuttgart LC3 ISO awl/plate-on-plate viscosity meter is with 40s -1Shearing rate measure viscosity.
With laser correlation spectrometry (Zetasizer 1000, Malvern Instruments, Herrenberg, Germany) the measurement mean particle size.
The OH value of being reported is calculated based on used monomer.
Acid number: the method according to DIN ISO 3682 is determined.
Embodiment 1
Add 469 grams 1 in 4 liters of multinecked flasks being furnished with mechanical stirring device, 6-hexylene glycol and 454 gram 6-caprolactones add 0.2 gram titanium tetraisopropylate again, use oil bath down this initially to be fed intake at inert gas flow (nitrogen) then and are heated to 110 ℃.In 15 minutes, in reaction mixture, add 401 gram methylcarbonates with pump, after this, mixture was kept 24 hours under refluxing.Under atmospheric pressure from reaction mixture, remove methylcarbonate and methanol mixture then, oil bath temperature was elevated to 150 ℃ from 110 ℃ continuously in 7 hours by distillation column.Oil bath temperature is dropped to 100 ℃ then, pressure drops to 20 millibars (absolute values), removes methyl alcohol and remaining methylcarbonate simultaneously.Subsequently oil bath temperature was elevated to 180 ℃ in 5 hours, and kept 2 hours in this temperature.With the reaction mixture cool to room temperature, add 0.2 gram dibutyl phosphate subsequently.The hydroxyl value of the polycarbonate diol of gained is 113 milligrams of KOH/ grams.
Embodiment 2
Repeat embodiment 1, different is 861 grams 1, and a 6-hexylene glycol and 0.2 a gram methyl ethyl diketone an ancient unit of weight equal to 20 or 24 *taels of silver (III) add 826 gram methylcarbonates as the initial adding that feeds intake with pump.Adding 0.2 gram dibutyl phosphate among the embodiment 1 saves.The hydroxyl value of the polycarbonate diol of gained is 109 milligrams of KOH/ grams.
Embodiment 3
Repeat embodiment 1, different is 616 grams 1, and 6-hexylene glycol, 1408 grams 1, a 4-butyleneglycol and 0.2 a gram methyl ethyl diketone an ancient unit of weight equal to 20 or 24 *taels of silver (III) add 2477 gram methylcarbonates as the initial adding that feeds intake with pump.Adding 0.2 gram dibutyl phosphate among the embodiment 1 saves.The hydroxyl value of the polycarbonate diol of gained is 113 milligrams of KOH/ grams.
Embodiment 4
To a top 60 of distillation additional unit, agitator and susceptor is housed and boosts and add 34,092 gram 3-methyl isophthalic acids in the power reactor in the time of 80 ℃, 5-pentanediol, 8.0 gram methyl ethyl diketone an ancient unit of weight equal to 20 or 24 *taels of silvers (III) and 10,223 restrain methylcarbonates.Subsequently with reaction mixture under nitrogen atmosphere at 2 hours internal heating to 150 ℃, and be elevated at stirring and backflow and pressure under the situation of 3.9 crust (absolute value) this temperature maintenance 2 hours.By distillation methyl alcohol is eliminated product as remove lasting 2.2 crust that descended altogether of pressure in this process of 4 hours with the mixture of methylcarbonate then.Finish still-process subsequently, pump into 10,223 gram methylcarbonates again in 150 ℃ of downhill reaction mixtures, reaction mixture is under stirring and refluxing, this temperature maintenance 2 hours, and pressure is elevated to 3.9 crust (absolute value).And then remove by the mixture that distillation is eliminated product and methylcarbonate with methyl alcohol, pressure continues to have descended altogether and 2.2 clings in this process of 4 hours.Finish distillation procedure subsequently, under 150 ℃, 7174 gram methylcarbonates be pumped in the reaction mixture, reaction mixture stir and reflux under this temperature maintenance 2 hours, pressure is elevated to 3.5 crust (absolute value).Then, the mixture of methyl alcohol being eliminated product and methylcarbonate by distillation is removed again, and pressure drops to normal atmosphere in this process of 4 hours.After this, with reaction mixture at 2 hours internal heating to 180 ℃, and under agitation this temperature maintenance 2 hours.Temperature is reduced to 130 ℃ subsequently, and makes nitrogen gas stream (5 liters/hour) by reaction mixture, in this process, pressure drops to 20 millibars.In 4 hours, temperature is elevated to 180 ℃ subsequently, and kept 6 hours in this temperature.And then the mixture of methyl alcohol and methylcarbonate removed from reaction mixture.
Inflation will be reacted the batch of material cool to room temperature, obtain colourless oligocarbonate diols liquid, and this product has following character:
Molecular weight, Mn 675 gram/moles
166.0 milligrams of KOH/ grams of OH value
Viscosity 6490mPa.s/23 ℃ and D:16
Embodiment 5
In 10 liters of reactors being furnished with stirring, cooling and heating unit, add the polycarbonate diols of 600 grams, and this is initially fed intake be heated to 143 ℃ from embodiment 1.Under this temperature, in 20 minutes, drip 7.75 gram di-t-butyl peroxides at 7.75 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow EuropeS.A., Horgen/Switzerland) solution in.Subsequently in 4.5 hours with uniform speed be metered into contain 81.5 the gram 2-EHAs, 566.5 the gram hydroxyethyl methylacrylates, 435 the gram butyl methacrylate, 567.5 the gram isobornyl methacrylates and 135 the gram cinnamic monomer mixture, meanwhile, be metered at 34.25 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow EuropeS.A., Horgen/Switzerland) solution of the 27.75 gram di-t-butyl peroxides in.About 20 minutes of this temperature maintenance.Subsequently in 1.5 hours with uniform speed be metered into contain 122.5 the gram methyl methacrylates, 172.75 the gram hydroxyethyl methylacrylates, 96 the gram butyl acrylates and 46.25 the gram acrylic acid monomer mixture, meanwhile, be metered at 25 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, DowEurope S.A., Horgen/Switzerland) solution of the 7.75 gram di-t-butyl peroxides in.Stirred 1 hour at 143 ℃ then, be cooled to 100 ℃ subsequently, add 29.25 gram N, the N-dimethylethanolamine.In homogenizing after 30 minutes, in 2 hours, at 80 ℃ with 3400 gram water-dispersion batch of materials.The gained copolymer dispersion has following character:
OH content (solid, calculated value) 4.3%
14 milligrams of KOH/ grams of acid number (solid)
Solids content 45.0%
Viscosity 850mPa.s/23 ℃
PH (in water, 10%) 8.5
Degree of neutralization 105%
Mean particle size 105 nanometers
Solubility promoter 1.1 weight %
Embodiment 6
In 10 liters of reactors being furnished with stirring, cooling and heating unit, add the polycarbonate diols of 600 grams, and this is initially fed intake be heated to 143 ℃ from embodiment 2.When this temperature, in 20 minutes, drip 7.75 gram di-t-butyl peroxides at 7.75 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow EuropeS.A., Horgen/Switzerland) solution in.Subsequently in 4.5 hours with uniform speed be metered into contain 81.5 the gram 2-EHAs, 566.5 the gram hydroxyethyl methylacrylates, 435 the gram butyl methacrylate, 567.5 the gram isobornyl methacrylates and 135 the gram cinnamic monomer mixture, meanwhile, be metered at 34.25 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow EuropeS.A., Horgen/Switzerland) solution of the 27.75 gram di-t-butyl peroxides in.With reaction mixture about 20 minutes in this temperature maintenance.Subsequently in 1.5 hours with uniform speed be metered into contain 122.5 the gram methyl methacrylates, 172.75 the gram hydroxyethyl methylacrylates, 96 the gram butyl acrylates and 46.25 the gram acrylic acid monomer mixture, meanwhile, be metered at 25 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow Europe S.A., Horgen/Switzerland) solution of the 7.75 gram di-t-butyl peroxides in.Stirred 1 hour at 143 ℃ then, be cooled to 100 ℃ subsequently, add 29.25 gram N, the N-dimethylethanolamine.In homogenizing after 30 minutes, in 2 hours, at 80 ℃ with 3625 gram water-dispersion batch of materials.The copolymer dispersion of gained has following character:
OH content (solid, calculated value) 4.3%
15 milligrams of KOH/ grams of acid number (solid)
Solids content 43.5%
Viscosity 400mPa.s/23 ℃
PH (in water, 10%) 8.5
Degree of neutralization 105%
Mean particle size 110 nanometers
Solubility promoter 1.0 weight %
Embodiment 7
In 6 liters of reactors being furnished with stirring, cooling and heating unit, add the polycarbonate diols of 600 grams, and this is initially fed intake be heated to 143 ℃ from embodiment 3.When this temperature, in 20 minutes, drip 7.75 gram di-t-butyl peroxides at 7.75 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow EuropeS.A., Horgen/Switzerland) solution in.Subsequently in 4.5 hours with uniform speed be metered into contain 81.5 the gram 2-EHAs, 566.5 the gram hydroxyethyl methylacrylates, 435 the gram butyl methacrylate, 567.5 the gram isobornyl methacrylates and 135 the gram cinnamic monomer mixture, meanwhile, be metered at 34.25 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow EuropeS.A., Horgen/Switzerland) solution of the 27.75 gram di-t-butyl peroxides in.With reaction mixture about 20 minutes in this temperature maintenance.Subsequently in 1.5 hours with uniform speed be metered into contain 122.5 the gram methyl methacrylates, 172.75 the gram hydroxyethyl methylacrylates, 96 the gram butyl acrylates and 46.25 the gram acrylic acid monomer mixture, meanwhile, be metered at 25 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow Europe S.A., Horgen/Switzerland) solution of the 7.75 gram di-t-butyl peroxides in.Stirred 1 hour at 143 ℃ then, be cooled to 100 ℃ subsequently, add 29.25 gram N, the N-dimethylethanolamine.In homogenizing after 30 minutes, in 2 hours, at 80 ℃ with 3625 gram water-dispersion batch of materials.The copolymer dispersion of gained has following character:
OH content (solid, calculated value) 4.3%
14 milligrams of KOH/ grams of acid number (solid)
Solids content 43.5%
Viscosity 2360mPa.s/23 ℃
PH (in water, 10%) 8.5
Degree of neutralization 105%
Mean particle size 130 nanometers
Solubility promoter 1.1 weight %
Embodiment 8
In 6 liters of reactors being furnished with stirring, cooling and heating unit, add the polycarbonate diols of 600 grams, and this is initially fed intake be heated to 143 ℃ from embodiment 4.When this temperature, in 20 minutes, drip 7.75 gram di-t-butyl peroxides at 7.75 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow EuropeS.A., Horgen/Switzerland) solution in.Subsequently in 4.5 hours with uniform speed be metered into contain 595.25 the gram hydroxyethyl methylacrylates, 487.75 the gram butyl methacrylate, 692.5 the gram isobornyl methacrylates and 135 the gram cinnamic monomer mixture, meanwhile, be metered at 34.25 gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow Europe S.A., Horgen/Switzerland) solution of the 27.75 gram di-t-butyl peroxides in.With reaction mixture about 20 minutes in this temperature maintenance.Subsequently in 1.5 hours with uniform speed be metered into contain 102.5 the gram methyl methacrylates, 173 the gram hydroxyethyl methylacrylates, 96 the gram butyl acrylates and 75 the gram acrylic acid monomer mixture, meanwhile, be metered into 25 the gram Dowanol PnB (propylene glycol mono-n-butyl ether; Solvent, Dow EuropeS.A., Horgen/Switzer--land) solution of the 7.75 gram di-t-butyl peroxides in.Stirred 1 hour at 143 ℃ then, be cooled to 100 ℃ subsequently, add 29.25 gram N, the N-dimethylethanolamine.In homogenizing after 30 minutes, in 2 hours, at 80 ℃ with 3500 gram water-dispersion batch of materials.The copolymer dispersion of gained has following character:
OH content (solid, calculated value) 4.4%
21 milligrams of KOH/ grams of acid number (solid)
Solids content 44.5%
Viscosity 1060mPa.s/23 ℃
PH (in water, 10%) 8.5
Degree of neutralization 105%
Averageparticle 94 nanometers
Solubility promoter 1.0 weight %
Embodiment 9: Comparative Examples (EP-A 0758007, and embodiment 1)
In 6 liters of reactors being furnished with stirring, cooling and heating unit, add 116 gram butyleneglycols and 150 gram Desmophen V218 (based on the polyethers of propylene oxide and glycerol, the OH value is 245 milligrams of KOH/ grams, BayerAG Leverkusen, Germany), this is initially fed intake is heated to 155 ℃.In this temperature, in 2 hours, be metered into 321 gram butyl acrylates, 366 gram vinylbenzene and 198 gram hydroxyethyl methylacrylates, meanwhile, be metered into the solution of 17.1 gram di-t-butyl peroxides in 28.6 gram butyleneglycols.In 1 hour, be metered into subsequently and contain 83 gram hydroxyethyl methylacrylates, 180 gram butyl acrylates, 139 gram vinylbenzene and the acrylic acid monomer mixture of 34 grams, meanwhile, be metered into 12.9 gram di-t-butyl peroxides in 21.4 gram butyleneglycols.Subsequently batch of material was stirred 2 hours at 150 ℃ to 155 ℃, be cooled to 100 ℃ then, add 50 gram dimethylethanolamines.In homogenizing after 30 minutes, in 2 hours, disperse with 1980 gram water at 80 ℃.The copolymer dispersion of gained has following character:
OH content (solid, calculated value) 3.2%
18 milligrams of KOH/ grams of acid number (solid)
Solids content 40%
Viscosity 830mPa.s/23 ℃
PH (in water, 10%) 9.4
Degree of neutralization 100%
Averageparticle is coated with 51 nanometers
Solubility promoter 4.0 weight %
Embodiment 10: Comparative Examples (EP 947557, and embodiment 3)
Add 186 gram butyleneglycols and 186 gram solvent naphthas in 6 liters of reactors being furnished with stirring, cooling and heating unit, this is initially fed intake is heated to 145 ℃.In this temperature, in 3 hours, be metered into contain 750 the gram methyl methacrylates, 125 the gram vinylbenzene, 445 the gram hydroxyethyl methylacrylates, 538 the gram butyl acrylates and 87 the gram butyl methacrylate mixture 1), in 1.5 hours, be metered at once then contain 128 the gram contain methyl methacrylate, 180 the gram hydroxyethyl methylacrylates, 100 the gram butyl acrylates and 60 the gram acrylic acid mixture 2).Meanwhile, in 5 hours, be metered into the solution of 88 gram di-t-butyl peroxides in 70 1: 1 blended butyleneglycol of gram and solvent naphtha.Stirred 2 hours at 145 ℃ then, be cooled to 100 ℃ then, add 76 gram dimethylethanolamines.In homogenizing after 30 minutes, in 2 hours, disperse with 2700 gram water at 80 ℃.The copolymer dispersion of gained has following character:
OH content (solid, calculated value) 3.3%
18 milligrams of KOH/ grams of acid number (solid)
Solids content 43.8%
Viscosity 1400mPa.s/23 ℃
PH (in water, 10%) 8.1
Degree of neutralization 105%
Averageparticle is coated with 110 nanometers
Solubility promoter 7.7 weight %
Embodiment 11
Polyisocyanate crosslinker
In 6 liters of reactors being furnished with stirring, cooling and heating unit, add 3500 gram Bayhydrol successively (the wetting ability aliphatic polyisocyanate, based on hexamethylene diisocyanate, BayerAG is Leverkusen) with 1500 gram Desmodur for XP 2570 (the low viscosity aliphatic polyisocyanate resin, based on hexamethylene diisocyanate, Bayer AG's XP 2410 Leverkusen), initially feeds intake this 30 ℃ of homogenizing 60 minutes.Add 37 gram Tinuvin then (Ciba is Basle) with 24 gram Tinuvin for 384-2 292 (Ciba, Basle), and then homogenizing 30 minutes.The isocyanate group content of the hydrophilic polyisocyanate mixtures of gained is 20.1%.
Application Example 12
Press described amount with component A and additive B yK 347 (silicone surfactant is used for improving the wettability of base material, Byk Chem, Wesel/ Germany) are mixed, and dilute with water.
Before applying, B component is distributed among the component A according to EP-A-0 685544 with the nozzle dispersion device, wherein the size of nozzle bore is 0.4 millimeter, pressure is 50 crust.With spray gun with blended 2K[two-pack] aqueous transparent paint vehicle paint modified with automotive OEM on the aluminium sheet (scrath resistance) and steel plate (chemical resistant properties) of known water-based surfacer and the precoating of black water priming paint.After applying, aluminium sheet and steel plate at room temperature dodge to be done 5 minutes, dodged at 80 ℃ and did 10 minutes, then 130 ℃ of dryings 30 minutes.The build of Clear coating is about 40 microns.
Table 1
Embodiment 12 a b c d e
Component A Parts by weight Parts by weight Parts by weight Parts by weight Parts by weight
Embodiment 10 (Comparative Examples) 411.9
Embodiment 9 (Comparative Examples) 339.9
Embodiment 5 356.4
Embodiment 6 372.1
Embodiment 7 370.4
Byk 347 2.3 2.2 2.2 2.2 2.3
Water 64.4 114.0 98.3 100.0 114.9
B component
Embodiment 11 119.5 125.6 125.6 125.6 141.1
Scrath resistance after 17 hours ％ ％ ％ ％ ％
Residual gloss is the residual gloss behind the levelling again 45 62 84 93 83 93 82 92 58 72
Chemical resistant properties ℃ ℃ ℃ ℃ ℃
The H of NaOH 1% concentration of distilled water 1% concentration 2SO 4 36 40 38 46 41 37 ＞68 44 38 ＞68 41 39 36 37 36
Scrath resistance
Scrath resistance test on the Clear coating is carried out according to DIN 55668.
The relative residual gloss of representing with % is represented the value compared according to glossiness [20 °] after DIN 5668 scrapings and the glossiness before the scraping.This value is high more, and scrath resistance is good more.
Chemical resistant properties
Chemical resistant properties is ℃ being unit representation.For this reason, make clear lacquer coating bear the sodium hydroxide solution of distilled water or 1% concentration respectively or the vitriolic of 1% concentration drips pouring, in the gradient baking oven, heat then.Measurement makes clear lacquer coating occur the temperature of visible damage for the first time.Temperature is high more, illustrates that clear lacquer chemical resistance of coating is good more.
Embodiment clearly illustrates that copolymer dispersion of the present invention can be used to prepare coating composition, and this coating composition is compared with the product of prior art, scrath resistance obviously better (residual gloss behind the levelling＞90% again), and chemical resistant properties is very good.
Though for the purpose of illustrating, the present invention is being described in detail in the preamble, but should understand, these write up only is in order to illustrate that those skilled in the art can make amendment to it under situation without departing from the spirit and scope of the present invention, and the present invention only is defined by the claims.

Claims (13)

1. aqueous copolymer dispersion, it comprises:
A) one or more hydroxyl-functional multipolymers and
B) one or more are as the hydroxyl-functional polycarbonate polyol of reactive thinner, wherein, A) by a), b), c) and d) come synthetic:
A) one or more do not contain (methyl) acrylate and/or the vinyl aromatic compounds of OH,
B) one or more hydroxyl-functionals (methyl) acrylate,
C) ionic and/or the potential ionic comonomer of free radicals copolymerization reaction can take place in one or more, and
D) Ren Xuan one or more are different from component a) to c) the monomer that free radicals copolymerization reaction can take place.
2. aqueous copolymer dispersion as claimed in claim 1 is characterized in that, hydroxyl-functional polycarbonate polyol B) the average hydroxy functionality be 1.6 to 6, number-average molecular weight is 240 to 5000Da.
3. aqueous copolymer dispersion as claimed in claim 1 is characterized in that, described hydroxyl-functional polycarbonate polyol B) by 1,4-butyleneglycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol or the preparation of their mixture.
4. aqueous copolymer dispersion as claimed in claim 2 is characterized in that, described hydroxyl-functional polycarbonate polyol B) by 1,4-butyleneglycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol or the preparation of their mixture.
5. aqueous copolymer dispersion as claimed in claim 1 is characterized in that, hydroxyl-functional polycarbonate polyol B) the average hydroxy functionality be 1.9 to 2.05.
6. aqueous copolymer dispersion as claimed in claim 2 is characterized in that, hydroxyl-functional polycarbonate polyol B) the average hydroxy functionality be 1.9 to 2.05.
7. aqueous copolymer dispersion as claimed in claim 3 is characterized in that, hydroxyl-functional polycarbonate polyol B) the average hydroxy functionality be 1.9 to 2.05.
8. aqueous copolymer dispersion as claimed in claim 4 is characterized in that, hydroxyl-functional polycarbonate polyol B) the average hydroxy functionality be 1.9 to 2.05.
9. the preparation method of the described aqueous copolymer dispersion of claim 1, described method comprises makes that one or more contain a), b), c) and monomer mixture d) at one or more hydroxyl-functional polycarbonate polyol B as reactive thinner) in the presence of carry out Raolical polymerizable, multipolymer with gained was scattered in the water before or after adding neutralizing agent subsequently, wherein
A) do not contain (methyl) acrylate and/or the vinyl aromatic compounds of OH for one or more,
B) be one or more hydroxyl-functionals (methyl) acrylate,
C) ionic and/or the potential ionic comonomer of free radicals copolymerization reaction can take place for one or more, and
D) be different from component a) to c for optional one or more) the monomer that free radicals copolymerization reaction can take place.
10. method as claimed in claim 9, it comprises:
I) make contain component a) to c) and optional d) monomer mixture at one or more hydroxyl-functional polycarbonate polyol B as reactive thinner) in the presence of carry out Raolical polymerizable, to form the hydroxyl-functional multipolymer, the OH value of described hydroxyl-functional multipolymer is a 12-200 milligram KOH/ gram solid, and acid number is a 0-50 milligram KOH/ gram solid; And
II) subsequently, to contain component a) to c) and optional d) monomer mixture in the reaction mixture that obtains by step (I), carry out Raolical polymerizable, to form the hydroxyl-functional multipolymer, the OH value of described hydroxyl-functional multipolymer is a 20-200 milligram KOH/ gram solid, and acid number is a 50-200 milligram KOH/ gram solid;
Wherein, to be enough to make the weight ratio of the hydroxyl-functional multipolymer that hydroxyl-functional multipolymer that step (I) obtains obtains step (II) be 10: 1 to 1: 2 to the amount of monomer of two kinds of monomer mixtures.
11. a water-based paint compositions, it comprises:
I) the described aqueous copolymer dispersion of one or more claims 1, and
Ii) one or more OH-active crosslinker.
12. a method for preparing coating, it comprises: will comprise on the coating composition paint base material of the described copolymer dispersion of claim 1, cure coating compositions subsequently is to form coating.
13. base material that is coated with the described coating composition of claim 1.
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DE19855167A1 (en) * 1998-11-30 2000-05-31 Basf Coatings Ag Coating composition consisting of at least three components, process for its production and its use
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CN101675132B (en) * 2007-05-04 2013-06-26 巴斯夫涂料有限公司 Water-based two-layer coating systems based on urethane, the use thereof and substrates coated with them
CN103347916A (en) * 2010-10-19 2013-10-09 拜耳知识产权有限责任公司 Aqueous preparation having soft-feel properties
CN103998479A (en) * 2011-12-22 2014-08-20 拜耳知识产权有限责任公司 Aqueous polyacrylate copolymer dispersions with high oh group content
CN103998479B (en) * 2011-12-22 2017-12-08 科思创德国股份有限公司 Water polyacrylic acid copolymer dispersion with high OH group contents
CN105593254A (en) * 2013-09-30 2016-05-18 Dic株式会社 Polycarbonate-modified acrylic resin, coating, and plastic molding coated with said coating
CN105593254B (en) * 2013-09-30 2017-10-27 Dic株式会社 Polycarbonate modified acrylic resin, coating and utilize the formed products after the paint spraying
US9969835B2 (en) 2013-09-30 2018-05-15 Dic Corporation Polycarbonate-modified acrylic resin, coating, and plastic molding coated with said coating
CN111683984A (en) * 2018-02-11 2020-09-18 科思创德国股份有限公司 Coating composition
CN115286985A (en) * 2022-01-24 2022-11-04 扬州工业职业技术学院 Double-component water-based environment-friendly coating

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DE502006007568D1 (en) 2010-09-16
CN1837251B (en) 2011-05-25
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KR20060097628A (en) 2006-09-14
RU2006106770A (en) 2007-09-20
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EP1702954A2 (en) 2006-09-20
US7550527B2 (en) 2009-06-23

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